Non-Traditional Machining (NTM) outperforms traditional processes by offering superior geometric and dimensional accuracy, along with a better surface finish. Photo Chemical Machining (PCM) represents one such NTM process, using chemical etching for material removal. PCM finds substantial application in the creation of microchannels in pharmaceutical, chemical and energy industries. Several input parameters—such as etchant concentration, etching time and etchant temperature—profoundly influence the machining’s quality and efficiency. Therefore, the optimization of these parameters is crucial. This study presents a comparative analysis of five Multiple Criteria Decision Making (MCDM) techniques—Technique for Order of Preference by Similarity to Ideal Solution (TOPSIS), Multi-Objective Optimization on the basis of Ratio Analysis (MOORA), Additive Ratio Assessment (ARAS), Weighted aggregated sum product assessment method (WASPAS) and Multi-Attributive Border Approximation Area Comparison Method (MABAC)—for the optimization of the PCM process. Key performance metrics considered are Material Removal Rate (MRR), Surface Roughness (SR), Undercut (Uc) and etch factor (EF). The weights of these criteria were calculated using the Criterion-Induced Aggregation Technique (CRITIC) and was compared with other popular methods like MEREC, Entropy and equal weights. MRR and EF are seen as beneficial criteria, while SR and Uc are perceived as cost criteria. Optimum process parameters were identified as 850 g/L etchant concentration, 40 min etching time and 70°C etchant temperature. Two of the three employed MCDM techniques agreed on these optimal parameters, reinforcing the findings. Furthermore, a strong correlation was observed amongst the employed MCDM techniques, further validating the results.